Luminescence of Donor‐Acceptor Pairs in Compounds of Yttrium and Scandium Oxides

The luminescence spectra of Sc₂O₃, Y₂O₃, and Y₂GeO₅ ceramics and thin films exposed to laser and cathode excitation were investigated. The investigation of the properties of longwave luminescence bands in Sc₂O₃ with maxima at 2.65, 2.35, and 2.05 eV, in Y₂O₃ with maxima at 2.60, 2.35, and 2.10 eV, and also in Y₂GeO₅ with maxima at 2.55, 2.25, and 2.00 eV point to the fact that they are caused by radiative recombination of the excited donoracceptor pairs Sc³⁺ (or Y³⁺)O^2–.     

Luminescence of Bismuth‐Activated Ceramics of Yttrium and Scandium Oxides

The luminescence spectra of Y₂O₃:Bi and Sc₂O₃:Bi ceramics have been investigated. The spectra have been resolved into elementary components by the Alentsev–Fock method. It has been established that the luminescence is attributed to emission centers of three types, two of which are due to the replacement of Y³⁺ (or Sc³⁺) by Bi³⁺ at the nodes of the crystal lattice of Y₂O₃ (or Sc₂O₃) with the point symmetry C ₂ and C _3i . The emission center Bi³⁺ in the position C_3i leads to the appearance of blue luminescence with maxima at 3.03 eV for Y₂O₃:Bi and at 3.05 eV for Sc₂O₃:Bi; this luminescence is attributed to the transition ³ P ₁–¹ S ₀. The emission center Bi³⁺ in the position C ₂ initiates green luminescence (which is also related to the ³ P ₁–¹ S ₀ transition in Bi³⁺) with a maximum in the region of 2.40 eV in Y₂O₃:Bi and in the region of 2.46 eV in Sc₂O₃:Bi. The red luminescence band with maxima at 1.85 eV in Y₂O₃:Bi and at 1.95 eV in Sc₂O₃:Bi is related to the presence of structural defects.     

Electrical properties and emission mechanisms of Zn-doped β-Ga2O3 films

We study the electrical properties and emission mechanisms of Zn-doped β-Ga₂O₃ film grown by pulsed laser deposition through Hall effect and cathodoluminescence which consist of ultraviolet luminescence (UV), blue luminescence (BL) and green luminescence (GL) bands. The Hall effect measurements indicate that the carrier concentration increases from 7.16×10¹¹ to 6.35×10¹² cm⁻³ with increasing a nominal Zn content from 3 to 7 at%. The UV band at 272 nm is not attributed to Zn dopants and ascribed as radiative electron transition from conduction band to a self-trapped hole while the BL band is attributable to defect level related to Zn dopant. The BL band has two emission peaks at 415 and 455 nm, which are ascribed to the radiative electron transition from oxygen vacancy (V_O) to valence band and recombination of a donor–acceptor pair (DAP) between V_O donor and Zn on Ga site (Zn_Ga) acceptor, respectively. The GL band is attributed to the phonon replicas’ emission of the DAP. The acceptor level of Zn_Ga is estimated to be 0.26 eV above the valence band maximum. The transmittance and absorption spectra prove that the Zn-doped β-Ga₂O₃ film is a dominantly direct bandgap material. The results of Hall and cathodoluminescence measurements imply that the Zn dopant in β-Ga₂O₃ film will form an acceptor Zn_Ga to produce p-type conductivity.     

Luminescence centers in yttrium silicate and germanate

Luminescence spectra for isostructural Y₂SiO₅ and Y₂GeO₅ are investigated. The spectra are resolved into elementary components by the Alentsev—Fock method. Bands with maxima in regions of 2.6, 2.3, and 2.05 eV in the spectra of Y₂SiO₅ luminescence and in regions of 2.55, 2.25, and 2.0 eV in the spectra of Y₂GeO₅ luminescence are considered as radiative recombination of excited associative donor-acceptor Y³⁺−O²⁻ pairs. The indicated bands are related to certain distances between yttrium (the donor) and oxygen (the acceptor). A band with a maximum of 2.95 eV in Y₂SiO₅ and 3.0 eV in Y₂GeO₅ occurs in recombination of electrons with holes trapped by an anionic sublattice. I. Franko L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 4, pp. 528–531, July–August, 1998.     

Photo- and thermostimulated processes in α-Al2O3

We reported on the recombination processes determined by the release of electrons from defects connected with the dosimetric 430 K thermostimulated luminescence (TSL) peak as well as with the 260 K TSL peak. These TSL peaks appear in thermochemically reduced α-Al₂O₃ crystals containing hydrogen and emission of these TSL peaks corresponds to luminescence of the F-center. The X-ray exposure or UV excitation in the absorption band of F-centers at 6.0 eV of reduced α-Al₂O₃ crystals doped with acceptor impurities results in the appearance of a broad anisotropic complex absorption band in the spectral region 2.5–3.5 eV and in the appearance of a predominant TSL peak at 430 K. Above 430 K the above-mentioned broad absorption band disappears. Optical bleaching of the 2.5–3.5 eV band is accompanied by the disappearance of the 430 K TSL peak and results in F-center emission. The X-ray or UV excitation of reduced α-Al₂O₃ crystals with donor-type impurities results in the appearance of an anisotropic absorption band at 4.2 eV and the appearance of a dominant TSL peak at 260 K. Above 260 K the 4.2 eV absorption disappears and photostimulated luminescence (PSL) of the F-center recombination luminescence in the 4.2 eV region is no longer observed. Optical bleaching of the 4.2 eV absorption band is accompanied by the disappearance of the 260 K TSL peak. The successful use of reduced α-Al₂O₃ in dosimetry needs the optimization of the concentration of all components (acceptors, hydrogen, intrinsic defects) involved in the thermo- and photostimulated processes.     

The role of Mg complexes in the degradation of InGaN-based LEDs

The electrical and optical properties of commercial blue InGaN-based LEDs after room temperature aging tests at DC-forward currents from 50 to 100 mA are studied by Current–Voltage, Capacitance–Voltage, Electroluminescence and Cathodoluminescence techniques. An increase of the reverse and low-bias forward currents, of the parasitic series resistance and a substantial optical intensity reduction are observed in all the devices investigated with or without heat sink. In addition, only in devices aged at 100 mA without heat sink, the onset of a broad optical band peaked at about 3.1 eV and an apparent doping decrease of about four times, as obtained by Capacitance–Voltage measurements, are found. Temperature-dependent luminescence analyses show the quenching of the 3.1 eV band above 200 K, suggesting its donor–acceptor-pair nature. The band onset is interpreted as a result of the Mg dopant instability in the p-type layers, correlated to the device self-heating inducing junction temperature above 300 C. The band is attributed to Mg-related metastable complexes, such as Mg–H₂, acting as shallow acceptors. Due to their unstable nature, the behaviour of the 3.1 eV emission is studied under controlled electron-beam irradiation in the SEM. Its time evolution during 60 min of irradiation reveals an almost complete quenching in the Cathodoluminescence spectra, which is attributed to the dissociation of the Mg–H₂ complexes.     

Electronic structure of an oxygen vacancy in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> from the results of Ab Initio quantum-chemical calculations and photoluminescence experiments

The electronic structure of an oxygen vacancy in α-Al₂O₃ and γ-Al₂O₃ is calculated. The calculation predicts an absorption peak at an energy of 6.4 and 6.3 eV in α-Al₂O₃ and γ-Al₂O₃, respectively. The luminescence and luminescence excitation spectra of amorphous Al₂O₃ are measured using synchrotron radiation. The presence of a luminescence band at 2.9 eV and a peak at 6.2 eV in the luminescence excitation spectrum indicates the presence of oxygen vacancies in amorphous Al₂O₃.     

The influence of oxygen vacancies on the chemical bonding in titanium oxide

A self-consistent LAPW band structure calculation for TiO_0.75 has been performed, assuming long-range order of vacancies on the oxygen sublattice. The calculation is based on a hypothetical model structure which can be described as Ti ₃ ^[4] Ti^[6]O_3o, where _o denotes an oxygen vacancy. In the model structure two types of titanium atoms occur: Ti^[4] atoms which have two vacancies as neighbours and are quadratically surrounded by four oxygen atoms, and Ti^[6] atoms which are octahedrally surrounded by six oxygen atoms. The calculated density of states (DOS) and the local partial densities of states are compared with the respective values for stoichiometric TiO containing no vacancies. A characteristic difference is the appearance of two sharp peaks in the DOS curve below the Fermi energy which are caused by the vacancies. These vacancy states exhibit a considerable amount of charge in the vacancy muffin-tin sphere and are found to be derived from Ti 3d states extending into the vacancy sphere. The introduction of vacancies also leads to a lowering of the Fermi energy indicating a stabilizing effect. The bonding situation in TiO_0.75 as compared to TiO as well as the changes in chemical bonding in the series TiC_0.75–TiN_0.75–TiO_0.75 are discussed on the basis of electron density plots. The loss of Ti^[4]–O bonds (as compared to TiO) is compensated by the formation of Ti^[4]–_o–Ti^[4] bonds across the vacancy and by an increase of the bond strength of the Ti^[4]–O bonds. On the other hand, the Ti^[4]–Ti^[4] and particularly the Ti^[4]–Ti^[6] bonds are weakened by the introduction of vacancies.Dedicated to Professor F. Kohler on the occasion of his 65^th birthday     

Behavior of copper in gallium arsenide with a high tellurium concentration

The electrophysical properties and cathode luminescence spectra of gallium arsenide with a high tellurium concentration (n = 2·10¹⁸ cm^–3) alloyed with copper are investigated under different diffusion conditions. Centers are determined from measurements of the Hall effect with an ionization energy of 0.190 ± 0.006 eV whose concentration does not depend on the arsenic vapor pressure (0.1 and 1 atm) and the cooling rate of the samples from the diffusion temperature. A band with h_m = 1.30–1.32 eV whose intensity depends on the cooling conditions of the samples was observed in the cathode luminescence spectra of these samples. The nature of the observed defects is discussed.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 93–99, July, 1979.In conclusion of this article the authors express their gratitude to L. K. Tarasova for preparation of the samples.     

Structural and optical properties of ZnO film by plasma-assisted MOCVD

High quality ZnO film was deposited by plasma-assisted metal-organic chemical vapor deposition (MOCVD). We observed a dominant peak at 34.6° due to (0 0 2) ZnO, which indicated that the growth of ZnO film was strongly C-oriented. The full-width at half-maximum (FWHM) of the -rocking curve was 0.56° indicating relatively small mosaicity. Photoluminescence (PL) measurement was performed at both room temperature and low temperature. Ultraviolet (UV) emission at 3.30 eV was found with high intensity at room temperature while the deep level transition was weakly observed at 2.513 eV. The ratio of the intensity of UV emission to that of deep level emission was as high as 193, which implied high quality of ZnO film. From PL spectrum at 10 K, we observed A-exciton emission at 3.377 eV and D°X bound exciton transition at 3.370 eV. The donor–acceptor transition and LO phonon replicas were observed at 3.333 and 3.241 eV respectively. Raman scattering was performed in back scattering at room temperature. The E₂, A_1(LO) and A_1(TO) mode was seen at 437.6, 575.8 and 380 cm^–1 respectively. In comparison with Raman spectrum of ZnO powder, we found that ZnO film was nearly free of strain, which indicated high crystal quality.     

Some physical properties of calcia and yttria stabilized ThO2 ceramics

In this paper the density, electrical conductivity, and dielectric permittivity of vacant ceramics of Ca _x Th_1–x O_2–x and Y _x Th_1–x O_2–x /2 type, respectivelly, were investigated as functions of temperature, frequency, and composition of these systems.The density drops with increasing calcium or yttrium amount, respectively. In the ThO₂-CaO system this is in agreement with the mechanism of formation of vacant phase Ca _x Th_1–x O_2x . The decrease of porosity in the ThO₂-Y₂O₃ system with increasing yttrium content can be due various factors which influence the mobility of Y³⁺ ions and, thus, also the formation of pores.The investigation of transport numbers has shown that whilst the Ca _x Th_1–x O_2–x phase under our experimental conditions is essentially p-type conductor, the Y _x Th_1–x O_2–x/2 phase is essentially ionic conductor.The transport of ion carriers is a diffusion-like process which has activation energy 1·28 to 1·16eV in the Ca _x Th_1–x O_2–x phase and 1·28 to 1·06 in the Y _x Th_1–x O_2–x /2 phase, respectively. The association of impurity ions with anion vacancies provides the maxima in conductivity isotherms.The relative dielectric permittivity of the vacant phase Ca _x Th_1–x O_2–x ranges from 19·2 to 36·2, in the phase Y _x Th_1–x O_2–x /2 from 19·2 to 103, depending on temperature, frequency, and composition of these systems.     

Nonradiative relaxation of photoexcited O<Stack><Subscript>1</Subscript><Superscript>0</Superscript></Stack> centers in glassy SiO<Subscript>2</Subscript>

The processes involved in the excited-state relaxation of hole O ₁ ⁰ centers at nonbridging oxygen atoms in glassy SiO₂ were studied using luminescence, optical absorption, and photoelectron emission spectroscopy. An additional nonradiative relaxation channel, in addition to the intracenter quenching of the 1.9-eV luminescence band, was established to become operative at temperatures above 370 K. This effect manifests itself in experiments as a negative deviation of the temperature-dependent luminescence intensity from the well-known Mott law and is identified as thermally activated external quenching with an energy barrier of 0.46 eV. Nonradiative transitions initiate, within the external quenching temperature interval, the migration of excitation energy, followed by the creation of free electrons. In the final stages, this relaxation process becomes manifest in the form of spectral sensitization of electron photoemission, which is excited in the hole O ₁ ⁰ -center absorption band.     

Luminescence centers in thin films of yttrium oxide and yttrium-aluminum garnet activated with bismuth

Luminescence spectra and photoluminescence excitation spectra of Y₂O₃:Bi and Y₃Al₅O₁₂:Bi thin films were investigated. Luminescence was stimulated by the emission from two types of centers that were associated with the substitution of Bi³⁺ for Y³⁺ in sites of the crystal lattice of Y₂O₃ (Y₃Al₅O₁₂) with point symmetries C₂ and C_3i (D₂ and C_3i). The emission of Bi³⁺ in the site with point symmetry C_3i causes blue luminescence in both Y₂O₃:Bi and Y₃Al₅O₁₂:Bi films with maxima at 3.03 eV and 3.15 eV, respectively, that is related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry C₂ gives green luminescence in Y₂O₃:Bi with the maximum at 2.40 eV that is also related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry D₂ leads to ultraviolet luminescence in Y₃Al₅O₁₂:Bi with the maximum at 3.75 eV that corresponds to the ³P₁-¹S₀ transition. The red luminescence band with the maximum at 1.85 eV in Y₂O₃:Bi is due to the presence of structural defects. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 202–207, March–April, 2008.     

Photoluminescence of zinc oxide modified by nanopowders

The modifying effect of Al₂O₃, Al₂O₃ · CeO₂, ZrO₂, ZrO₂ · Y₂O₃ nanopowders on the photoluminescence spectra of ZnO powder in the 360–660 nm range is investigated. It is found that the introduction of nanoparticles causes a decrease in the ultraviolet band intensity and an increase in the visual spectral band intensity. The change in the intensity of elementary components of the visible range band during modification seems to be explained by the emergence of oxygen and zinc vacancies (V _O⁺ and V _Zn⁻) and interstitial oxygen ions (O _i ⁻).     

XES studies of La-Sr-Cu-O and Y-Ba-Cu-O ceramics

X-ray emission spectroscopic studies of superconducting ceramics characterised by the following compositions: La_2.19Sr_0.07Cu_1.05O_x, Y_0.9Ba_1.8Cu_3.3O_y and Y_0.9Ba_2.0Cu_3.1O_y, as well as of a semiconducting ceramic, Y_1.9Ba_1.0Cu_1.1O_z, have been performed using spectrometers of an electron probe microanalyser. Concentrations of the superconducting phases and semiconducting one exceeded 80% of the whole sample compositions. The CuL spectra detected for superconducting samples revealed a satellite maximum connected with Cu³⁺ ions lying at+1.4 eV in the high energy side of the spectrum. Mean valence of copper ions in the La–Sr–Cu–O sample has been estimated to be +2.16 and for the Y_0.9Ba_2.0Cu_3.1O_y, sample above+2.1. It was confirmed that the binding energy of 3d electrons taking part in the electronic transition involving this satellite maximum and the main one is equal to 3.5 eV. The satellite at+2.6 eV is connected with states close to the Fermi level, and the satellite caused by theM _2,3 M _4,5 M _4,5 super Coster-Kronig transition at about 4.2 eV has been established. Analysis of the LaL₄ spectrum showed evidence for weak bonding between the lanthanum ions and oxygen ions.     

Luminescent properties of erbium-activated glasses

The spectra, intensity, and duration of trivalent erbium luminescence in a large number of inorganic glasses of various compositions were investigated. The observed absorption and luminescence bands were attributed to transitions between certain^sL_j levels of the Er³⁺ ion. It is shown that in all cases the principal portion of the luminescence yield was associated with the⁴I_13/2 ⁴I_15/2 transition band with _max = 6500 cm^–1. The effects of glass composition, activator concentration, and temperature on the yield and duration of luminescence in the 6500 cm^–1 band were studied. An investigation of the effect of temperature on the structure of this band was used to construct a diagram of the crystalline splitting of the⁴I_13/2 and⁴I_15/2 levels in glass.     

The optical gap of NiO

The nature of the optical absorption gap in NiO at 4.0 eV is investigated. It is found that this gap is due to a band to band transition, where an electron is taken out of the valence band and placed into the conduction band. The optical gap of 6.0 eV found in NiMgO is of a nature, where an electron is taken out of the oxygen 2p band and placed into the first affinity level of the Ni²⁺ ion (3d ⁸L»3d ⁹L^–1). The impurity band created in Ni_1–x Li _x O by the Li ions is found 2.3 eV below the bottom of the conduction band in agreement with model predictions.     

Luminescence of excitons in single-crystal garnets

Comparative studies of the luminescence of Y₃Al₅O₁₂:Ce and Lu₃Al₅O₁₂:Ce single-crystal films and their volume analogues—Y₃Al₅O₁₂ and Y₃Al₅O₁₂:Ce single crystals, excited by synchrotron radiation with energy E=120–150 eV, have been performed. The films were grown from melt-solution by liquid-phase epitaxy and the crystals were grown from melt. The single-crystal films and single crystals studied are characterized by different degrees of structural order, in particular, different concentrations of substitutional defects of the Y _Al ³⁺ and LU _Al ³⁺ types. It was ascertained that the bands at 260 and 250 nm in the intrinsic luminescence spectra of Y₃Al₅O₁₂:Ce and Lu₃Al₅O₁₂:Ce single-crystal films and single crystals are due to the emission of self-trapped excitons. The luminescence band with λ_max=300 nm and τ=0.36 μs, which is present in the luminescence spectrum of single crystals and absent in the spectra of single-crystal films, is due to the recombination of electrons with holes localized at Y _Al ³⁺ centers. It is shown that an efficient energy transfer by excitons to activator ions occurs in Y₃Al₅O₁₂ and Lu₃Al₅O₂ single-crystal films doped with Ce³⁺ ions.     

Effect of Y2O3 addition on the conductivity and elastic modulus of (CeO2)1 − x(YO1.5)x

The conductivity and elastic modulus of (CeO₂)_1 − x(YO_1.5)_x for x values of 0.10, 0.15, 0.20, 0.30, and 0.40 were investigated by experiments and molecular dynamics simulations. The calculated conductivity exhibited a maximum value at approximately 15 mol% Y₂O₃; this trend agreed with that of the experimental results. In order to clarify the reason for the occurrence of the maximum conductivity, the paths for the transfer of oxygen vacancies were counted. The numerical result revealed that as the content of Y₂O₃ dopant increases, the number of paths for the transfer of oxygen vacancies decreases, whereas the number of oxygen vacancies for conductivity increases. Thus, the trade-off between the increase in the number of vacancy sites and the decrease in the vacancy transfer was considered to be the reason for the maximum conductivity occurring at the Y₂O₃ dopant content of approximately 15 mol%. The calculated elastic modulus also exhibited a minimum value at approximately 20 mol% Y₂O₃, which also agreed with the experimental results. It was shown that the Y–O–Y bonding energy increased with the increasing content of Y₂O₃ dopant. Thus, the trade-off between the increase in the number of vacancy sites and that in the Y–O–Y bonding energy was considered to be the reason for the minimum elastic modulus occurring at the Y₂O₃ dopant content of approximately 20 mol%.     

Photoluminescence quenching in zinc oxide modified by Al2O3 and Al2O3 · CeO2 Nanopowders under proton irradiations

The photoluminescence spectra of initial ZnO powder and that modified by Al₂O₃, Al₂O₃ · CeO₂ nanopowders are investigated in the range 360–660 nm before and after 100-keV proton irradiation. It is found that the introduction of nanoparticles causes a decrease in the UV-band intensity and a change in the luminescence bands in the visual spectrum due to V _O ⁺ oxygen vacancies, O _int ^- interstitial oxygen, and V _Zn ^- zinc vacancies. Luminescence quenching in the UV and visible spectra occurs under the effect of protons. The decomposition of the spectra into elementary defects and analysis of changes in their integrated intensity during modification and irradiation of the powders are carried out.